Electrochemistry Communications 4 (2002) 593–598 www.elsevier.

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Electric double layer capacitance of highly pure single-walled carbon nanotubes (HiPcoe Buckytubese) in propylene carbonate electrolytes
Soshi Shiraishi *, Hideyuki Kurihara, Keiji Okabe, Denisa Hulicova, Asao Oya
Department of Chemistry, Faculty of Engineering, Gunma University, Tenjin-cho 1-5-1, Kiryu, Gunma 376-8515, Japan Received 11 April 2002; received in revised form 17 May 2002; accepted 17 May 2002

Abstract The double layer capacitance of highly pure single-walled carbon nanotubes (SWCNTs) prepared by the HiPcoe process was measured in 1:0 mol dmÀ3 LiClO4 /propylene carbonate solution. The unpurified SWCNT electrode was mainly composed of a bundle structure of SWCNTs with around 1.0 nm tube diameter, small amount of amorphous carbons, and Fe catalyst particles. The Fe catalysts in the surface of the SWCNT were removed by immersion in HClaq . The as -SPE analysis of the N2 adsorption isotherms revealed that both the SWCNTs before and after the immersion in HClaq had relatively high specific surface areas of $ 500 m2 gÀ1 without microporosity although the tube ends were closed. The SWCNTs showed a gravimetric capacitance of around 45 F gÀ1 . Thus, the specific capacitance per unit surface area was estimated to be around 10 lF cmÀ2 , which was higher than that of conventional activated carbon fibers. Furthermore, the capacitance of the SWCNTs did not decrease even at high current density. This good rate property of the SWCNTs is related to the large area of the external surface ($ 400 m2 gÀ1 ) on which ion adsorption/desorption can proceed fast because of no ion sieving. On the other hand, most of the Fe catalyst in the SWCNT could be removed by thermal oxidation followed by immersion in HClaq . However, the gravimetric capacitance of this purified SWCNT was not as great as that expected by the correlation of 10 lF cmÀ2 . This is related to the formation of amorphous carbons caused by the thermal oxidation. Ó 2002 Elsevier Science B.V. All rights reserved.
Keywords: Single-walled carbon nanotube; Electric double layer capacitance; Nonaqueous electrolyte; Thermal oxidation

1. Introduction New porous carbon materials have been desired for improving the energy density of electric double layer capacitors (EDLC) [1]. Carbon nanotubes (CNTs) have attracted much attention as new carbon materials since their discovery by Ijima [2]. CNTs are ideal porous carbons with a cylindrical shape since the tube inside can be considered to have a very uniform pore with a nm size. In fact, the double layer capacitance of the CNT has already been reported in many references [3–10]. Especially, the single-walled carbon nanotube (SWCNT) [11] is one of the most attractive CNTs for
* Corresponding author. Tel.: +81-277-30-1352; fax: +81-277-301353. E-mail addresses: ssiraisi@chem.u.ac.jp, ssiraisi@gunma.u.ac.jp (S. Shiraishi).

EDLC electrode materials, because the SWCNT has a theoretically high surface area (the total specific surface area of the outside plane and the inside plane of the CNT is 2630 m2 gÀ1 ). Moreover, the well-defined/bent graphene sheet of the SWCNT may exhibit a higher specific capacitance compared with the other carbon materials such as activated carbons, graphite, etc. According to the literature [7–10], the reported values for the gravimetric double layer capacitance of the SWCNT electrode were over a wide range between 20 and 300 F gÀ1 . For example, Bard and co-workers [7] estimated the capacitance of the SWCNT in acetonitrile electrolyte to be around 280 F gÀ1 . On the other hand, Baughman and co-workers [8] showed a smaller capacitance in the NaCl aqueous electrolyte (20–40 F gÀ1 ) of the pure SWCNT prepared by laser abrasion. The capacitance in a KOH aqueous electrolyte, reported by Beguin and co-workers [9], was 40 F gÀ1 , while that by

1388-2481/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved. PII: S 1 3 8 8 - 2 4 8 1 ( 0 2 ) 0 0 3 8 2 - X

Experimental 2. The SWCNT electrode for the double layer capacitance measurement was prepared from the unpurified HiPcoe Buckytubese in the following ways. tion in air and the following washing process in HClaq to completely remove the Fe catalyst. the sample were immersed in 6 M HClaq for 2 h under sonication and then filtered through a microporous PTFE membrane and washed in pure water and methanol. / Electrochemistry Communications 4 (2002) 593–598 Lee and co-workers [10] was 180 F gÀ1 . Lot No. This paper-like sample is referred to as ‘‘SWCNTunp ’’ hereafter. The SWCNT prepared by the HiPcoe process is very different from the other SWCNTs prepared such as the arc discharge [11. Activated carbon fibers (ACFs) were used as reference samples for correlation between the specific surface area and the double layer capacitance. The first one was the SWCNTunp washed with HClaq . Recently. The capacitor using a nonaqueous electrolyte such as a propylene carbonate solution is used for energy storage. The washing process involved immersion of the SWCNTunp electrode in 6 M HClaq for 24 h to remove the Fe catalyst on the surface of the SWCNT. JSM5100.1. Characterization of SWCNT electrode 2. This sample (referred to as ‘‘SWCNTHCl ’’) after the immersion was washed with pure water and dried in vacuum at 200 °C for 3 h. JEOL. The HiPcoe Buckytubese contain a small amount of the metallic Fe catalyst [13].2. the correlation between the surface area and the double layer capacitance of this highly pure SWCNT in nonaqueous electrolyte is discussed and compared with traditional activated carbon fibers. This inconsistency may be due to the difference in the kinds of electrolytes and the low purity of the SWCNT. In this paper. Sample preparation An unpurified single-walled carbon nanotube (HiPcoe Buckytubese.13] and this pure SWCNT has been commercialized by Carbon Nanotechnologies (USA) under the trade name of ‘‘HiPcoe Buckytubese’’. The second purified sample was obtained by thermal oxidaThe SWCNT electrodes were characterized using a scanning electron microscope (SEM. a highly pure SWCNT was prepared by the thermal decomposition of CO under high pressure with an Fe catalyst [12. The Fe content and the bulk density are also shown in Scheme 1. Fe content. This washed sample was dispersed in 500 ml of methanol under ultrasonics and filtered again using the microporous membrane to obtain a paper-like sample (referred to as ‘‘SWCNTox-HCl ’’ hereafter). Shiraishi et al. Preparation procedure. the exact specific capacitance of the CNT in a nonaqueous electrolyte is very important and has to be clarified. Scheme 1. The ACFs were prepared by the carbonization and steam-activation of phenolic resin fibers. 2. A 100 mg sample of the HiPcoe Buckytubese was dispersed in 500 ml of methanol under sonication for 2 h. The dispersed nanotubes were filtered through membrane of porous PTFE film to form an accumulated layer of SWCNT. and bulk density of various SWCNT electrodes. The preparation procedure of the ACFs is described in our previous papers [16–18]. . 10518-53156) was obtained from Carbon Nanotechnologies. The above preparation scheme is shown in Scheme 1. Therefore. which is similar to that described in the literature [13]. Two kinds of purified SWCNT electrodes were also prepared from the unpurified HiPcoe Buckytubese. After oxidation. it is still difficult to understand the capacitance of the SWCNT. The bulk density of these electrodes was also estimated by measuring their areas and thicknesses. The HiPcoe Buckytubese (100 mg) were oxidized in humid air at 225 °C for 5 h.14] or by laser abrasion [15] with respect to the point of purity and tube diameter. The SWCNT ‘‘HiPcoe Bucktubese’’ be considered as one of the most suitable materials for understanding the true properties of the double layer capacitance for SWCNTs because of its high purity. The sample was dried for 1 h at 60 °C and then was peeled off the membrane filter to obtain a paper-like sample. Therefore. called ‘‘Bucky Paper’’.594 S. The Fe content of the above three electrodes was estimated by TG analysis in dry air and the ICP analysis of the ash (Fe2 O3 ).

Japan) was used as the nonaqueous electrolyte for the double layer capacitance measurement.34 nm and close to that of graphite. Shiraishi et al. The as plot-SPE method cannot only separate the information about the micropores and the other pores. Japan).0 nm. 1 shows the SEM images of the SWCNT electrodes. JEOL. (a) SWCNTunp . The double layer capacitance of a single SWCNT electrode was measured by using a three-electrode cell in a pure argon glove box. The water content was less than 30 ppm. The SWCNT electrodes were pressed into a Ti mesh as current collector. No particles or flakes of impurities were observed even in the unpurified SWCNT electrode.1. but also effectively prevent the overestimation problem of the specific surface area. In the XRD measurement. Japan) at 77 K. The SWCNT electrodes with the Ti mesh were immersed in the electrolyte under a reduced pressure (> 103 Pa) for 12 h for degassing. 2(b) for the SWCNTHCl electrode was almost the same as the SWCNTunp . . Japan). there are no sharp diffraction lines of graphite.0 M LiClO4 /PC. and (b) SWCNTox-HCl . SEM images of SWCNTs. Bel Japan. Kishida Chemicals. The XRD pattern in Fig. The tube diameter and the Fe catalyst size are in good agreement with that reported by Smalley and co-workers [13].3. 1. which is very different from other unpurified SWCNTs prepared by the arc-discharge method or laser abrasion method. SEM observations Fig.S. / Electrochemistry Communications 4 (2002) 593–598 595 Japan). RINT 2100V/PC.2. Kaneko and co-workers [20] have already applied the as plot-SPE method to pore structure analysis of single-walled carbon nanohorns (SWCNHs). Therefore. the paper-like sample (1 Â 1 cm2 ) was attached to the nonreflective sample holder. The capacitance was estimated from a chronopotentiogram obtained using a galvanostatic method. 2 shows the XRD patterns for the SWCNT electrodes.2 nm). The diffraction lines attributed to the triangle lattice of the SWCNT and cubic lattice of metallic Fe were observed in Fig. 3. the diffraction angle of the 10 line of the SWCNT suggests that the tube diameter is around 1. The N2 adsorption/desorption isotherms were measured by a N2 adsorption/desorption system (BELSORP28SA. corresponding to typical bucky paper composed of highly pure SWCNT. Supposing that the van der Waals space between tubes is 0. The full width half maximum of the Fe(1 1 1) line and the Scherrer equation revealed that the lattice size of the Fe catalysts was estimated to be around 3 nm. Electric double layer capacitance measurements A propylene carbonate solution containing 1:0 mol dmÀ3 LiClO4 (1. however. These results suggested that the immersion process in HClaq did not Fig. XRD patterns Fig. it can be said that the SWCNTunp electrode is mainly composed of SWCNT and Fe catalysts. Rigaku. 3. 2. A weak and broadened line assigned to amorphous carbon was observed around $26° in the XRD pattern. JEM-1200EXS. The specific surface area and the pore structure parameters were estimated by analysis of the isotherms by the as plot-SPE method [19]. X-ray diffractometer (XRD. The double layer capacitance of the activated carbon fiber electrode was also measured in the same way as in the previous papers [16–18]. This diameter is smaller than that of the SWCNT prepared by the arc-discharge method or the laser abrasion (> around 1. 2(a) for the SWCNTunp electrode. The detailed procedure for this measurement is described in the previous papers [16–18]. and transmission electron microscope (TEM. Results and discussion 3. All electrodes were composed of only bundles with several tens nanometer diameter.

This may be due to the small diameter of the HiPcoe Buckytubese. The SEM image in Fig. Surface and pore structure analysis The N2 adsorption isotherms (not shown here) of the SWCNTunp and the SWCNTHCl were similar and classified as type II. and (b) SWCNTHCl .3. 3. XRD (CuKa) patterns of various SWCNTs. The results corresponded to the XRD pattern in Fig. TEM images of SWCNTs. For the SWCNTox-HCl . but the amount of N2 adsorption at the low relative pressure was greater than those of the SWCNTunp and the SWCNTHCl . In the other hand. 2(b) showed the maintenance of the tube bundle structure in the SWCNTox-HCl . (a) SWCNTunp . and (c) SWCNTox-HCl . Shiraishi et al.596 S. On the other hand. but simultaneously caused damage to the tube structure. 2. and (b) SWCNTox-HCl . Fig. Therefore.4. / Electrochemistry Communications 4 (2002) 593–598 3. The surface area and the pore structure were estimated by these N2 adsorption isotherms. the XRD pattern of the SWCNTox-HCl electrode exhibited a decrease in the intensity of the diffraction lines for the Fe catalyst and the growth of the broadened line of amorphous carbon. . (a) SWCNTunp . The bundle structure consisting of SWCNT and many dark spots of the Fe catalyst particles are observed in the TEM image of the SWCNTunp . there are only a few Fe catalyst particles. The oxidation stability of the HiPcoe Buckytubese is very different from that of the SWCNTs prepared by the arc-discharge or the laser abrasion [13]. change the SWCNT structure and the crystallinity. 3 shows the TEM images of the SWCNTunp and the SWCNTox-HCl . 3. It is confirmed by the small decrease in the Fe content shown in Scheme 1. these results indicate that some tubes in each bundle decomposed to amorphous carbon. This means the SWCNTox-HCl has some microporosity. The SWCNTox-HCl also showed a kind of type II isotherm. which indicate nonporous materials. Fig. but amorphous carbon was contained in the outer part of the SWCNT bundle shown in the black circle. the Ref-ACFs showed type I isotherms of a highly microporous carbon. TEM observations Fig. 2(c) and suggested that the HiPcoe Buckytubese were unstable to the thermal oxidation even at a low temperature such as 225 °C. The purification process with the oxidation effectively removed the Fe catalyst. No intensity change of the Fe diffraction line is due to the only removal of the Fe catalyst exposed on the surface.

was much smaller than the theoretical tube inside surface area (% 1315 m2 gÀ1 ).75 Wmicro (nm) 0. This linearity suggested that the specific capacitance per surface area of the Ref-ACF was around 5:5 lF cmÀ2 . 3. and average inicropore width of SWCNTs and Ref-ACFs Sample SWCNTunp SWCNTHCl SWCNTox–HCl . Correlation between total specific surface area (estimated by as -SPE method) and double layer capacitance in 1. In the case of the SWCNTox-HCl .78 0. Probably. The capacitance of the ACFs such as Ref-ACF(10) and (60) were much smaller than that expected from the gradient of 5:5 lF cmÀ2 . The as -SPE method provides separate structure information about the micropores and the external surface (containing mesopores and macopores surface). a Number in parenthesis means the activation duration (min). and average micropore width for the SWCNT samples and the reference ACF samples are summarized in Table 1. (240). 2 ! 4 Vvs:Li=Liþ ) for various SWCNTs and Ref-ACFs. In the case of the Ref-ACFs. The difficulty in the accessibility of gas adsorption may be concerned with the surface functionalitiy formation on the tube end or the self-closing of the tube end during the curing process after the thermal oxidation.27 0.66 0. micropore volume.S. rather than the stability of the tube end-cap to thermal oxidation. changes in the micropore surface and the micropore volume were observed. and (480) seemed to be linear with respect to the total surface area. Wmicro : average micropore width estimated by as -SPE method (Slit like-pore model). The average micropore width (wmicro ) of the SWCNTs before the purification mainly indicates the size of the inter-space between each tube. many tube ends are still closed or inside the opened tube is not accessible for gas adsorption. Shiraishi et al. The gravimetric capacitance of the SWCNTunp and the SWCNTHCl was around 45 F gÀ1 and smaller than that of the well-activated ACFs. micropore volume. which are derived from the opening of the tube end or the formation of amorphous carbons with some microporosity. . the micropore specific surface area (Smicro ) was much greater than that of the external specific surface area (Sext ).094 0. but probably influenced by the micropore size of the amorphous carbon parts. the micropore surface area of the SWCNTox-HCl . Vmicro : pore volume of micropore estimated by as -SPE method. According to our previous research [16– 18]. which was smaller than that of the ACFs such as Ref-ACF(10) or Ref-ACF(60).0 M LiClO4 /PC (galvanostatic: 40 mA gÀ1 . The capacitance of the well-activated ACFs such as Ref-ACF(120). However. 4.015 0. The total specific surface area (Stotal ) and the micropore volume (Vmicro ) of the SWCNT electrodes were lower than those of the RefACFs. Especially. which is greater than that of not Fig.64 0. while the micropore surface area of the SWCNTs was smaller than the external one.52 0.40 0. The average micropore width of the SWCNTox-HCl was comparable with the Ref-ACFs.59 0. 4 shows the correlations between the total surface area and the gravimetric capacitance for the SWCNTs and Ref-ACFs. Sext : specific surface area of external surface (containing mesopore and macropore) estimated by as -SPE method. the external surface area of the SWCNTunp and the SWCNTHCl accounted for most of the total surface area accessible for gas adsorption.67 0. / Electrochemistry Communications 4 (2002) 593–598 Table 1 Specific surface area. The specific surface area.36 0.72 0.79 597 Stotal : Sext þ Smicro . However. the specific capacitance per surface area was about 10 lF cmÀ2 .44 0. Double layer capacitance behavior of the SWCNTs Fig. Ref-ACF(10)a Ref-ACF(60) Ref-ACF(120) Ref-ACF(240) Ref-ACF(480) Stotal ðm2 gÀ1 Þ 462 489 782 870 1119 1341 1664 1938 Sext ðm2 gÀ1 Þ 387 401 545 30 22 36 26 44 Smicro ðm2 gÀ1 Þ 75 88 241 840 1097 1305 1638 1894 Vmicro ðml gÀ1 Þ 0.023 0.5. this deviation is due to the ion sieving effect of the micropores that prevents an ion from going into the micropore network. Smicro : specific surface area of micropore estimated by as -SPE method. positive process.

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